Tandem transfer hydrogenation and oligomerization for hydrocarbon production

ABSTRACT

A method for coupling an alkane with an alkene using a hydrogen transfer catalyst and an alkene dimerization catalyst to form one or more higher molecular weight hydrocarbons.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 61/753,768, filed on Jan. 17, 2014, which isincorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The disclosure relates to hydrocarbon production by hydrogenation andoligomerizaton and, more particularly, to catalysis of alkanes andalkenes by a tandem transfer hydrogenation and oligomerization.

BACKGROUND

Light alkane gases (ethane, propane, butane) and low-boiling liquids(pentane, hexane, etc.) represent a considerable proportion ofpetroleum-derived hydrocarbons. These light alkanes are found in naturalgas and petroleum reservoirs, and also generated as low-value byproductsof refinery processes such as catalytic cracking as well as inFisher-Tropsch conversion of synthesis gas. The latter processes mayalso produce corresponding alkenes; streams containing substantialamounts of both alkane and alkene are commonly obtained. These lighthydrocarbons have limited value as useful fuels, particularly in thetransportation sector, which generally requires heavier hydrocarbons. Asthe cost of raw petrochemicals rises due to increased demand and ananticipated reduction in supply, and concern over carbon emissions leadsto demands for increased energy efficiency, a method to convert theseunder-utilized light hydrocarbons into more valuable heavier productswould greatly impact the production of chemical fuels.

SUMMARY

The disclosure provides methods and compositions to convert a mixture ofhydrocarbons into a mixture of heavier hydrocarbons. In a simplifiedversion, a mixture of an alkane and an alkene (which may or may not havethe same carbon number) are coupled to give an overall increase of theaverage carbon number of the product components. This is accomplishedthrough the action of two catalysts that act concurrently. In oneembodiment, a first catalyst (“hydrogenation catalyst”) is a transferhydrogenation catalyst. For example, a hydrogenation catalyst suitablefor transfer hydrogenation includes, but is not limited to, solubleorganometallic species containing a metal from group 9; these samespecies immobilized on a solid support such as silica or alumina; andplatinum group metals dispersed on a suitable support. In oneembodiment, a suitable hydrogenation catalyst comprises formula I:

wherein, each R is independently H or a (C₁-C₃₀)hydrocarbyl radical;each R¹ is independently a (C₁-C₃₀)hydrocarbyl radical; and each X isindependently an O or CH₂.

This hydrogenation catalyst serves to dehydrogenate the alkane reactantsto alkenes, and to use the resulting H₂ to hydrogenate alkenes toalkanes. The alkenes may be sacrificial additives, or the products ofthe process itself. The second catalyst (“dimerization catalyst”)effects alkene dimerization or oligomerization; dimers/oligomers can bea coupling of identical monomers (“homodimers/oligomers”) or a couplingof similar, but not identical, monomers (“heterodimers/oligomers”).Exemplary dimerization catalysts include, but are not limited to,soluble organometallic species; supported versions of these samespecies; and zeolitic materials containing group 10 metal ions. In oneembodiment, a suitable dimerization catalyst comprises Formula II:

wherein, Z is either 1 or 2; n is an integer from 1 to 5; each Y isindependently selected from D, H, optionally substituted (C₁-C₆)alkyl,silane, and (C₁-C₄)alkylsilane; Y¹ is a H, D, halo, ═S, ═O, PMe₃, ═C(H)(CMe₃); Y² is a H, D, halo, ═S, ═O, PMe₃, or absent; R² is a H, aryl,optionally substituted (C₁-C₁₅)alkyl, or an optionally substituted(C₂-C₂₅)hetero-alkyl; and R³ is a H, aryl, optionally substituted(C₁-C₁₅)alkyl, or an optionally substituted (C₁-C₁₅)hetero-alkyl. Inanother embodiment, the dimerization catalyst comprises the Formula II(a):

wherein, R² is an aryl, optionally substituted (C₁-C₁₅)alkyl, or anoptionally substituted (C₁-C₁₅)hetero-alkyl. This catalyst converts theC_(n) alkenes, present in the reactant mixture and/or formed bydehydrogenation catalysis, selectively into C_(2n) or higher alkenes.

In a particular embodiment, the disclosure provides a method of couplingan alkane with an alkene so as to form one or more higher molecularweight hydrocarbons, comprising: coupling an alkane (e.g., a straightchain (C₅-C₁₀)alkane) with an alkene (e.g., a straight chain(C₅-C₁₀)alkene) in the presence of catalysts comprising: (i) a hydrogentransfer catalyst and (ii) an alkene dimerization catalyst so as togenerate one or more higher molecular weight hydrocarbons (e.g., alkanesor alkenes); wherein the hydrogen transfer catalyst is an iridium pincercomplex catalyst and the alkene dimerization catalyst is tantalumcatalyst, wherein the one or more higher molecular weight hydrocarbonscomprise one or more carbon atoms from both the alkane and the alkene.In a further embodiment, both the hydrogen transfer catalyst and thedimerization catalyst are heterogeneous catalysts. In yet a furtherembodiment, the dimerization catalyst comprises a structure of FormulaII:

wherein, Z is either 1 or 2; n is an integer from 1 to 5; each Y isindependently selected from D, H, optionally substituted (C₁-C₆)alkyl,silane, and (C₁-C₄)alkylsilane; Y¹ is a H, D, halo, ═S, ═O, PMe₃, ═C(H)(CMe₃); Y² is a H, D, halo, ═S, ═O, PMe₃, or absent; R² is a H, aryl,optionally substituted (C₁-C₁₅)alkyl, or an optionally substituted(C₁-C₁₅)hetero-alkyl; and R³ is a H, aryl, optionally substituted(C₁-C₁₅)alkyl, or an optionally substituted (C₁-C₁₅)hetero-alkyl. Inanother embodiment, the dimerization catalyst comprises a structure ofFormula II(a):

wherein, R² is an aryl, optionally substituted (C₁-C₁₅)alkyl, or anoptionally substituted (C₁-C₁₅)hetero-alkyl. In yet another embodiment,the hydrogen transfer catalyst comprises a structure of Formula I:

wherein, each R is independently H or a (C₁-C₃₀)hydrocarbyl radical;each R¹ is independently a (C₁-C₃₀)hydrocarbyl radical; and each X isindependently an O or CH₂. In a further embodiment, the hydrogentransfer catalyst comprises a structure of Formula I(a):

In a particular embodiment, for the methods disclosed herein, thehydrogen transfer catalyst is immobilized on a solid support, whereinthe reaction is carried out in a solvent, and wherein the method furthercomprises the step of separating the free hydrogen transfer catalystfrom the solvent.

In a certain embodiment, for the methods disclosed herein, the hydrogentransfer catalyst is immobilized on a solid support, wherein thereaction is carried out in a solvent, and wherein the method furthercomprises the step of separating free hydrogen transfer catalyst fromthe solvent.

In a particular embodiment, the disclosure provides a method forcoupling a first alkane with a second alkane to form one or more highmolecular weight hydrocarbons, comprising: coupling a first alkane(e.g., a straight chain (C₅-C₁₀)alkane) with a second alkane (e.g., astraight chain (C₅-C₁₀)alkane) using a sacrificial hydrogen acceptor inthe presence of catalysts comprising: (i) a hydrogen transfer catalystand (ii) an alkene dimerization catalyst so as to generate one or morehigher molecular weight hydrocarbons (e.g., alkanes or alkenes); whereinthe hydrogen transfer catalyst is an iridium pincer complex catalyst andthe alkene dimerization catalyst is tantalum catalyst, wherein the oneor more higher molecular weight hydrocarbons comprise carbon atoms fromthe first alkane and the second alkane. In a further embodiment, thesacrificial hydrogen acceptor is styrene, tert-butylethylene or acombination thereof. In yet a further embodiment, the first alkane andthe second alkane have the same structure. In an alternate embodiment,the first alkane and the second alkane do not have the same structure.

In a certain embodiment, for the methods disclosed herein, the hydrogentransfer catalyst and the dimerization catalyst are heterogeneouscatalysts. In a further embodiment, the dimerization catalyst comprisesa structure of Formula II:

wherein: Z is either 1 or 2; n is an integer from 1 to 5; each Y isindependently selected from D, H, optionally substituted (C₁-C₆)alkyl,silane, and (C₁-C₄)alkylsilane; Y¹ is a H, D, halo, ═S, ═O, PMe₃, ═C(H)(CMe₃); Y² is a H, D, halo, ═S, ═O, PMe₃, or absent; R² is a H, aryl,optionally substituted (C₁-C₁₅)alkyl, or an optionally substituted(C₁-C₁₅)hetero-alkyl; and R³ is a H, aryl, optionally substituted(C₁-C₁₅)alkyl, or an optionally substituted (C₁-C₁₅)hetero-alkyl. Inanother embodiment, the dimerization catalyst comprises a structure ofFormula II(a):

wherein, R² is a phenyl. In yet another embodiment, the hydrogentransfer catalyst comprises a structure of Formula I:

wherein, each R is independently H or a (C₁-C₃₀)hydrocarbyl radical;each R¹ is independently a (C₁-C₃₀)hydrocarbyl radical; and each X isindependently an O or CH₂. In a further embodiment, the hydrogentransfer catalyst comprises a structure of Formula I(a):

In a particular embodiment, for the methods disclosed herein thehydrogen transfer catalyst is immobilized on a solid support, whereinthe reaction is carried out in a solvent system, and wherein the methodfurther comprises the step of separating free hydrogen transfer catalystfrom the solvent. In a further embodiment, the solvent system comprisesthe first alkane and/or the second alkane.

In another embodiment, for the methods disclosed herein, the methodfurther comprises the step of hydrogenating or reducing the one or morehigher molecular weight hydrocarbons made by the methods disclosedherein.

The disclosure further provides for a liquid hydrocarbon fuel comprisingthe one or more higher molecular weight hydrocarbons made by the methodsdisclosed herein.

The disclosure also provides for an apparatus for carrying out themethods of the disclosure, which comprises an inlet and an outlet; and abed or column comprising a hydrogen transfer catalyst and a dimerizationcatalyst disclosed herein. In yet a further embodiment, for the bed orcolumn comprising the catalysts: (i) the hydrogen transfer catalyst isimmobilized on a solid support; and (ii) the dimerization catalyst isimmobilized on a solid support.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1. A time evolution plot of the tandem catalytic coupling of1-hexene/n-heptane. Top: Reaction conditions and products observed (“1”denotes dimerization catalyst; “2” denotes hydrogenation catalysts).Bottom left: Time course plot for concentrations of all observedspecies. Bottom right: Expansion and simplification showing formation ofC₁₂ (from 1-hexene dimerization) and n-hexane (from 1-hexene/n-heptanetransfer hydrogenation). Points are from tandem reactions, while blackhollow points represent several individual catalytic runs with either 1(diamonds) or 2 (squares). These data indicate that the rates of theindividual catalytic reactions are identical to the rates observedduring tandem catalysis, and therefore the two catalysts operateindependently.

FIG. 2. A time evolution plot of the tandem catalytic coupling of thedimerization of 1-hexene (240 mM) catalyzed by 1 (8 mM) at 100° C.(three runs).

FIG. 3. Initial rate of formation of the major regioisomer fromdimerization of 1-hexene (248-3996 mM) catalyzed by 1 (8 mM) at 100° C.(each line generated by linear regression of an overlay of at leastthree runs).

FIG. 4. Top: Plot of initial rate (k_(obs)) for 1-hexene dimerization(points represented by diamonds: major isomer; points represented bysquares: minor isomer) catalyzed by 1 (8 mM) at 100° C. versus[1-hexene]₀ (248 mM-3996 mM; data from Table 1), indicating an approachto saturation. Bottom: Corresponding double-reciprocal plot to calculatevalues for K_(eq), k₁, and k₂K_(eq)′ according to equations 1-8.

FIG. 5. Left: van't Hoff plot (80° C.-125° C.) for the equilibriumCp*TaCl₂(1-hexene) (A) +1-hexene

Cp*TaCl₂ (metallacycle) (B) governed by K_(eq), with thermodynamicparameters. Right: Eyring plot (80° C.-125° C.) for the unimoleculardecomposition of Cp*TaCl₂ (metallacycle) (B into C) governed by k₁, withactivation parameters.

FIG. 6. Rates of 1-hexene/n-decane transfer hydrogenation and 1-hexeneisomerization catalyzed by 2 at 100° C. versus initial[1-hexene](248-1010 mM). The data clearly show inverse order in 1-hexenefor transfer hydrogenation, and positive order in 1-hexene forisomerization.

FIG. 7. Plot of ln([styrene]) versus time for the dimerization ofstyrene (250 mM) catalyzed by 1 (8 mM) at 100° C. through 4 half-lives(two runs, final 160 h data point not included in linear correlation).

FIG. 8. Reaction progress for entry 7 (Table 4). Legend: ♦: styrene; ▪:ethylbenzene; ▴: heptane dimers; ⋄: co-dimers; ◯: styrene dimer. Linesare drawn as visual guides only.

FIG. 9. Comparison of transfer hydrogenation progress in the conversionof styrene (diamonds) to ethylbenzene (squares) for catalysis with 2only (unshaded diamonds and squares, dashed lines) and with 1 and 2 intandem (shaded diamonds and squares, solid lines; values corrected forstyrene converted to co-dimers and styrene dimers).

FIG. 10. Linear correlation of response factors versus carbon number.

FIG. 11. GC trace of the dimerization of 1-hexene to produce C₁₂ dimers.

FIG. 12. Time course plot of the dimerization of 1-hexene by 1 (overlayof three runs).

FIG. 13. Initial rate of 1-hexene dimerization as a function of[1-hexene]₀ at 80° C. Top: Rate vs.

FIG. 14. Initial rate of 1-hexene dimerization as a function of[1-hexene]₀ at 80° C. Top: Rate vs. concentration. Bottom: Doublereciprocal plot. Legend: diamond, 1-hexene; square, dimer product.

FIG. 15. Initial rate measurements for 1-hexene dimerization at 90° C.Top: Major isomer product. Bottom: Minor isomer product. Legend:diamond, 1-hexene; square, dimer product.

FIG. 16. Initial rate of 1-hexene dimerization as a function of[1-hexene]₀ at 90° C. Top: Rate vs. concentration. Bottom: Doublereciprocal plot. Legend: diamond, 1-hexene; square, dimer product.

FIG. 17. Initial rate measurements for 1-hexene dimerization at 100° C.Top: Major isomer product. Bottom: Minor isomer product. Legend:diamond, 1-hexene; square, dimer product.

FIG. 18. Initial rate measurements for 1-hexene dimerization at 110° C.Top: Major isomer product. Bottom: Minor isomer product. Legend:diamond, 1-hexene; square, dimer product.

FIG. 19. Initial rate of 1-hexene dimerization as a function of[1-hexene]₀ at 100° C. Top: Rate vs. concentration. Bottom: Doublereciprocal plot. Legend: diamond, 1-hexene; square, dimer product.

FIG. 20. Initial rate of 1-hexene dimerization as a function of[1-hexene]₀ at 110° C. Top: Rate vs. concentration. Bottom: Doublereciprocal plot. Legend: diamond, 1-hexene; square, dimer product.

FIG. 21. Initial rate measurements for 1-hexene dimerization at 125° C.Top: Major isomer product. Bottom: Minor isomer product.

FIG. 22. Initial rate of 1-hexene dimerization as a function of[1-hexene]₀ at 125° C. Top: Rate vs. concentration. Bottom: Doublereciprocal plot. Legend: diamond, 1-hexene; square, dimer product.

FIG. 23. Initial rate measurements for 1-hexene/n-decane transferhydrogenation at 100° C. Top: n-Hexane formation (hydrogenation).Bottom: 2-Hexenes formation (isomerization).

FIG. 24. Initial rate measurements for 1-hexene/n-decane transferhydrogenation at 125° C. Top: n-Hexane formation (hydrogenation).Bottom: 2-Hexenes formation (isomerization).

FIG. 25. Initial rate of 1-hexene hydrogenation and isomerization by 2(5 mM) versus [1-hexene]₀. Top: 100° C. Bottom: 125° C.

FIG. 26. GC trace of styrene (500 mM) dimerization by 1 (25 mM), 110°C., 72 h.

FIG. 27. Initial ¹H NMR spectrum of styrene (500 mM) dimerization by 1.

FIG. 28. ¹H NMR spectrum of styrene (500 mM) dimerization by 1 (25 mM),110° C., 72 h.

FIG. 29. ¹H NMR spectrum of the dimerization of styrene with 1 (t=0 h,initial).

FIG. 30. ¹H NMR spectrum of the dimerization of styrene with 1 (t=42 h,˜50%).

FIG. 31. ¹H NMR spectrum of the dimerization of styrene with 1 (t=160 h,final point).

FIG. 32. Stack plot of ¹H NMR spectra (2.5-6.7 ppm) for styrenedimerization catalyzed by 1 at 100° C. Nineteen spectra were taken atthe following time points: 0, 1, 2, 4, 7, 10, 18, 24, 32, 42, 52, 64,72, 88, 97, 109, 119, 134, and 160 hours (t=0 h at bottom).

FIG. 33. ¹H NMR spectrum of Cp*TaCl₂(styrene)³ in C₆D₆, establishingchemical shifts for comparison to catalytic runs.

FIG. 34. Consumption of styrene during dimerization catalyzed by 1 at100° C. and 125° C. monitored by ¹H NMR spectroscopy (two runs). Top:Conc. plot. Bottom: In plot. Legend: diamond, concentration of styreneat 100° C.; square, concentration of styrene at 125° C.

FIG. 35. Initial rates of styrene/1-heptene co-dimerization with 1. Datafor each time point was collected from 3 different vials, giving 12 datapoints for each initial rate determination.

FIG. 36. GC trace of the co-dimerization of styrene (250 mM) and1-heptene (250 mM) with 1 (25 mM) to produce co-dimers. The C₁₄ products(1-heptene dimers) are assigned based upon the work of McLain et al. (J.Am. Chem. Soc. 102:5610 (1980)); the co-dimers are assigned based onGC/MS and comparison to authentic samples of three of the proposedcompounds (vide infra). The styrene/1-nonane co-dimer (peak at 11.102min) is assigned based on GC/MS, and its regiochemistry by analogy tothe major isomer of the styrene/1-heptene co-dimers. The 1-nonane ispresumably generated from coupling 1-heptene and ethylene (from 1).

FIG. 37. GC/MS trace of the co-dimerization of styrene (250 mM) and1-heptene (250 mM) with 1 (25 mM) to produce co-dimers. Mass spectrumcorresponds to indicated peak.

FIG. 38. GC/MS trace of the co-dimerization of styrene (250 mM) and1-heptene (250 mM) with 1 (25 mM) to produce co-dimers. Mass spectrumcorresponds to indicated peak.

FIG. 39. GC/MS trace of the co-dimerization of styrene (250 mM) and1-heptene (250 mM) with 1 (25 mM) to produce co-dimers. Mass spectrumcorresponds to indicated peak.

FIG. 40. GC/MS trace of the co-dimerization of styrene (250 mM) and1-heptene (250 mM) with 1 (25 mM) to produce co-dimers. Mass spectrumcorresponds to indicated peak.

FIG. 41. GC/MS trace of the co-dimerization of styrene (250 mM) and1-heptene (250 mM) with 1 (25 mM) to produce co-dimers. Mass spectrumcorresponds to indicated peak.

FIG. 42. GC/MS trace of the co-dimerization of styrene (250 mM) and1-heptene (250 mM) with 1 (25 mM) to produce co-dimers. Mass spectrumcorresponds to indicated peak.

FIG. 43. GC trace of the nickel-catalyzed co-dimerization of styrene and1-heptene to generate the major product shown. The 1-heptene dimers andstyrene dimer are assigned based on GC/MS (vide infra). Theregiochemistry of the styrene dimer for this Ni-catalyst was similar tothat presented by Ho et al. (Angew. Chem. Int. Ed. 49:9182 (2010)).

FIG. 44. GC/MS trace of the nickel-catalyzed co-dimerization of styreneand 1-heptene. Mass spectrum corresponds to indicated peak.

FIG. 45. GC/MS trace of the nickel-catalyzed co-dimerization of styreneand 1-heptene. Mass spectrum corresponds to indicated peak.

FIG. 46. GC/MS trace of the nickel-catalyzed co-dimerization of styreneand 1-heptene. Mass spectrum corresponds to indicated peak.

FIG. 47. Top: Reproduction of FIG. 43 (bottom). Middle: Reproduction ofFIG. 36 (bottom). Bottom: GC trace of the co-injection ofstyrene/1-heptene co-dimerization reactions effected by 1 and the insitu generated Ni-catalyst. The peaks marked with “Ta” are from thetantalum-catalyzed reaction, and those marked with “Ni” are from thenickel-catalyzed reaction. The red arrow highlights that the co-dimerpeak at 10.29 min (middle trace) corresponds to the2-phenyl-3-methylene-octane product.

FIG. 48. Plots of reaction progress over time for Entry 7 in Table 4.Top: Overlay of both data sets. Bottom: Expansion of productconcentration range. Lines are drawn as visual guides.

FIG. 49. Overlay of reaction progress for runs from Entry 7 in Table 4(filled points), and styrene/n-heptane transfer hydrogenation catalyzedby only 2 (hollow points). Only styrene and ethylbenzene concentrationsare shown for clarity. The styrene concentration for the tandemreactions was corrected by compensating for the amount of styreneconsumed in dimerization reactions to form either styrene dimers orstyrene/n-heptane co-dimers.

DETAILED DESCRIPTION

As used herein and in the appended claims, the singular forms “a,” “an,”and “the” include plural referents unless the context clearly dictatesotherwise. Thus, for example, reference to “a catalyst” includes aplurality of such catalysts and reference to “the alkane” includesreference to one or more alkanes and so forth.

Also, the use of “or” means “and/or” unless stated otherwise. Similarly,“comprise,” “comprises,” “comprising” “include,” “includes,”“including,” “have,” “haves,” and “having” are interchangeable and notintended to be limiting.

It is to be further understood that where descriptions of variousembodiments use the term “comprising,” those skilled in the art wouldunderstand that in some specific instances, an embodiment can bealternatively described using language “consisting essentially of” or“consisting of.”

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood to one of ordinary skill inthe art to which this disclosure belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice of the disclosed methods and compositions, the exemplarymethods, devices and materials are described herein.

As exploitation of traditional crude oil reserves becomes economicallyand geopolitically more volatile, and concern regarding CO₂ emissionsfrom the current inefficient use of carbon-based energy carriersincreases, many countries and industries are actively pursuing alternatefuel sources. These factors are driving the development of newtechnologies for fuel production from carbon sources such as bitumen andkerogen (so-called oilsands and shale oil), natural gas, andlignocellulosic biomass. In contrast to fuels derived from crude oilthat are collected by fractional distillation, obtaining hydrocarbons inthe desired weight range from these alternate carbon sources oftenrequires extensive refining and synthetic manipulation, such ascatalytic cracking and Fischer-Tropsch synthesis using syngas. Inaddition to the optimal fuel-range hydrocarbons (C₈-C₂₂), lighteralkanes and alkenes are abundant by-products of these processes.Currently, these light hydrocarbons have little value as fuels due totheir volatility and low volumetric energy density. This inherentinefficiency in fuel production will increase both the economic andenvironmental cost of continued exploitation of these emerging carbonsources.

In order to better utilize low carbon number energy carriers, thesefeedstocks need to be upgraded to higher molecular weight compounds,ideally in the diesel fuel-range (C₁₀-C₂₂). Such a process mustnecessarily perform chemistry on alkanes under relatively mildconditions: the entropic cost of coupling smaller carbon chains intolarger ones means that high temperatures are potentiallythermodynamically incompatible. One possible technology for achievingthis goal is alkane metathesis. Alkane metathesis operates via combinedalkane dehydrogenation and alkene metathesis using either two separatecatalysts, or one catalyst capable of both transformations. In the idealcase, two C_(n) alkanes afford one C_(2n-2) alkane and one equivalent ofethane in an approximately thermoneutral reaction; however, alkanemetathesis tends toward a statistical carbon number distribution ofalkanes, with few examples that can achieve any selectivity for thedesired C_(2n-2) product. While further catalyst development efforts mayresult in a viable process, alternative methods for upgrading lighthydrocarbons are also needed.

The disclosure provides an approach toward light hydrocarbon upgradingbased on a tandem alkane dehydrogenation and alkene dimerization. Thismethod takes advantage of the mixed nature of many light by-productstreams by incorporating both alkanes and alkenes as substrates. In anideal system (shown for a linear alkane and 1-alkene in Scheme I), onecatalyst would dimerize the alkene component of the mixed feedstock to aC_(2n) alkene. Subsequent transfer hydrogenation by a second catalystwould convert the alkane component to a 1-alkene, while hydrogenatingthe C_(2n) product to an alkane. The 1-alkene thus formed is thencatalytically dimerized with a second equivalent of 1-alkene, and thecycle continues; the net reaction is coupling of alkane and alkene tohigher alkane, with no by-products generated. Calculations indicate thatsuch a reaction is thermodynamically favored below ˜250° C.; therefore,catalysts for both dimerization and transfer hydrogenation must operatewith appreciable rates at relatively mild temperatures.

The disclosure demonstrates this process using a dual homogeneouscatalytic system in which a dimerization catalyst (1) comprises astructure of Formula II effects alkene dimerization, and alkane/alkenetransfer hydrogenation is carried out by a hydrogenation catalyst. Thesecatalysts function in tandem to affect alkane/alkene coupling.

In a particular embodiment, hydrogen transfer catalyst (2) comprises astructure of Formula I:

wherein, each R is independently H or a (C₁-C₃₀)hydrocarbyl radical;each R¹ is independently a (C₁-C₃₀)hydrocarbyl radical; and each X isindependently an O or CH₂.

In a further embodiment, hydrogen transfer catalyst (2) comprises astructure of Formula I(a):

In a particular embodiment, dimerization catalyst (1) comprises astructure of Formula II:

wherein, Z is either 1 or 2; n is an integer from 1 to 5; each Y isindependently selected from D, H, optionally substituted (C₁-C₆)alkyl,silane, and (C₁-C₄)alkylsilane; Y¹ is a H, D, halo, ═S, ═O, PMe₃, ═C(H)(CMe₃); Y² is a H, D, halo, ═S, ═O, PMe₃, or absent; R² is a H, aryl,optionally substituted (C₁-C₁₅)alkyl, or an optionally substituted(C₁-C₁₅)hetero-alkyl; and R³ is a H, aryl, optionally substituted(C₁-C₁₅)alkyl, or an optionally substituted (C₁-C₁₅) hetero-alkyl.

In another embodiment, dimerization catalyst (1) comprises a structureof Formula II(a):

wherein, R² is an aryl, optionally substituted (C₁-C₁₅)alkyl, or anoptionally substituted (C₁-C₁₅)hetero-alkyl.

Ta-based alkene dimerization catalyst having the general Formula II wereused in the Examples presented herein. Cp*TaX₂(alkene) complexes arereported to be “indefinitely active” for the selective dimerization of1-alkenes to two regioisomers at temperatures up to 100° C. (see SchemeII below); they are inert to internal alkenes and the product1,1-disubstituted alkenes. In addition, no co-catalyst or activator isrequired.

As described above, the disclosure provides a dual homogeneous catalyticsystem for alkane/alkene coupling based on an early/late transitionmetal dichotomy: alkene dimerization is effected by a dimerizationcatalyst (1) comprising the structure of Formula II or Formula II(a),while transfer hydrogenation is performed by a hydrogen transfercatalyst (2) comprising the structure of Formula I of Formula I(a). Thissystem is capable of coupling, for example, 1-hexene and n-heptane witha high degree of catalyst cooperativity. This system operates by asacrificial H₂ acceptor pathway, in which the alkene substrate, and notthe C_(2n) product, acts as the hydrogen acceptor (Scheme III). Thus,for every equivalent of alkane upgraded, one equivalent of a differentalkane is generated as a byproduct. An additional feature of this systemis that in most cases the alkene substrate can also function as acoupling partner: for example, in 1-hexene/n-heptane mixtures,competitive homodimerization of 1-hexene generates a substantial amountof C₁₂, along with C₁₃ resulting from the coupling of 1-hexene and1-heptene (generated via transfer hydrogenation).

Both catalysts operate independently, with no mutual inhibition ordecomposition over the course of the reaction (see FIG. 1). For example,kinetic studies reveal that 1-hexene dimerization catalyzed by thedimerization catalyst of Formula II exhibits positive order (<1)dependence on [1-hexene], with an approach to saturation at highconcentrations; additionally, the dimerization rate increases verylittle with temperature. In stark contrast, the rate of1-hexene/n-heptane transfer using the hydrogenation catalyst of FormulaI has inverse order dependence on [1-hexene], and increasessubstantially with temperature. These opposing kinetic features lead toan imbalance in the relative rates of these two processes as either theconcentration of 1-hexene is raised, or the reaction temperature israised. In an effort to identify other alkene/alkane combinations thatare amenable to tandem catalysis, the use of styrene has been studied asa sacrificial hydrogen acceptor for alkane dimerization. By attenuatingthe ratio of the two catalysts, a high degree of selectivity (>26:1) fortandem catalysis in this styrene/alkane system can be realized.

The disclosure also provides a in-depth kinetic study of thedimerization of 1-hexene catalyzed by dimerization catalyst 1 (see,Scheme I-III) at elevated temperatures and low initial substrateconcentrations. The catalyst of Formula II (e.g., Cp*TaCl₂(alkene)complexes) undergo rapid decomposition at 100° C. in the absence ofadded alkene. Thus, catalyst decomposition at these elevatedtemperatures should be especially problematic at low concentrations of1-alkene, since these conditions would favor Cp*TaCl₂(alkene) as thecatalyst resting state. It is surprising, then, that the tandemcatalytic alkane/alkene coupling operates at exactly this set ofconditions with no apparent catalyst decomposition, even over >30 hourswith 1-alkene added slowly via syringe pump (see Examples, below).

Thus, an aspect of the disclosure is that the transferhydrogenation/dimerization occurs in a single-stage tandem process. Inone particular version the C_(n) alkene reactant is dimerized bydimerization catalyst 1 (comprising a structure of Formula II or II(a))to generate a new C_(2n) alkene product. This C_(2n) alkene is convertedto the C_(2n) alkane by transfer hydrogenation with hydrogenationtransfer catalyst 2 (comprising a structure of Formula I or I(a)); thesource of hydrogen in this case is the C_(n) alkane reactant. Thisgenerates a C_(n) alkene, which will undergo dimerization withdimerization catalyst 1 having the structure of Formula II or II(a),producing more C_(2n) alkene. This process would continue until all ofthe alkene equivalents are consumed and converted to the C₂ alkane. Forsimplicity Scheme IV shows a single isomer of the product, but adifferent isomer or a mixture of two or more might resultpreferentially, depending on the choice of dimerization catalyst 1.

This tandem process can also be applied to a number of alternatetransformations, such as combining transfer hydrogenation witholigomerization, such that the reaction of one molecule of C_(n) alkanewith x molecules of C_(n) alkene would result in a C_((x+1)n) alkane. Itmay also be possible to effect conversion of two (or more) molecules ofC_(n) alkane to higher alkanes, either by carrying out the reaction inthe presence of a sacrificial hydrogen acceptor, such as an alkene thatcannot undergo oligomerization or another species; or by devisingconditions such that the H₂ liberated during transfer dehydrogenationcan be separated from reactant and products.

In order for this tandem process to occur, the two catalysts are presentin the same reactor, and retain their activity under the reactionconditions needed to effect both transformations. This is accomplishedby careful choice of the two catalysts such that mutual or individualdeactivation does not occur. For example, in a batch reaction, bothcatalysts are dissolved and/or suspended in the reaction mediumcontaining or consisting of the alkane/alkene mixture. In a flowreactor, the two catalysts would be supported on the same solid, or twosolid catalysts would be intimately mixed, and the alkane/alkenereactants passed over this dual catalyst as either a gas or liquid.

The specific examples below have been successfully carried out,demonstrating the feasibility of the disclosed process. The disclosurethus, provides a homogeneous dual Ta/Ir catalyst system can affect bothselective coupling of alkane/alkene mixtures and dimerization of alkanesto branched alkene products with a high degree of cooperation.Additional modification can include modifying the Ir catalyst and/or byselecting a different dimerization catalyst to produce less branchedalkene isomers; these latter products may be more desirable from a fuelsstandpoint as well.

Example 1

General Considerations:

All experiments were performed under an argon inert atmosphere usingstandard Schlenk line, high-vacuum line, or glovebox techniques.Solvents for routine syntheses (pentane, toluene, diethyl ether,tetrahydrofuran (THF), were dried by passage through activated alumina,degassed under vacuum by several freeze-pump-thaw cycles, and storedover activated 4 Å molecular sieves under an inert atmosphere. n-Heptanefor use in catalytic reactions (HPLC grade, >99%, Sigma-Aldrich) waspre-dried by stirring ˜400 mL over CaH₂ (˜10 g) for at least 48 hours.The solvent was then vacuum transferred onto “titanocene” (˜1 g) andstirred overnight; the solution remained black-green throughout. Then-heptane was collected from this titanocene solution by a final vacuumtransfer and stored under an argon atmosphere. 1-Hexene, 1-heptene, andneohexene (isoprene-free) were distilled under argon from CaH₂ afterstirring for several days.

NMR Spectroscopy:

Spectra were acquired on a Varian Mercury 300 MHz instrument with arelaxation delay time of 2 seconds. Spectra were processed in thefollowing way using MestReNova: automatic baseline correction, automaticphase correction, exponential apodization along t1 of 1.00 Hz, andautomatic linear correction applied to the integrals.

GC Analysis:

Gas chromatography was performed on an Agilent 6890N instrument using aflame ionization detector and a DB-1 capillary column (10 m length, 0.10mm diameter, 0.40 μm film). Runs used the following program: hold at 35°C. for 2 minutes, ramp temperature at 2° C. min⁻¹ to 50° C., hold at 50°C. for 2 minutes, ramp temperature at 100° C. min⁻¹ to 290° C., hold at290° C. for 5 minutes.

Response factors for linear hydrocarbons ranging from C₅ to C₁₈ versusadamantane were determined by the following procedure. Two standardsamples were prepared containing known amounts of ten compounds(n-pentane, 1-hexene, n-heptane, n-octane, 1-dodecene, 1-tridecene,1-tetradecene, 1-hexadecene, n-octadecane, and adamantane) dissolved indichloromethane. Analysis of these two solutions by GC generated dataused to calculate individual response factors for each compound versusadamantane using the following formula:Resp.factor=([Area_(analyte)]×[mmol_(adamantane)])/([Area_(adamantane)]×[mmol_(analyte)])

The following response factors were obtained:

Run 1 Run 2 n-Pentane 0.3947 0.3979 1-Hexene 0.4970 0.5158 n-Heptane0.6250 0.6320 n-Octane 0.7215 0.7364 1-Dodecene 1.1945 1.20611-Tridecene 1.3309 1.3274 1-Tetradecene 1.4134 1.3967 1-Hexadecene1.6722 1.6639 n-Octadecane 1.8343 1.8544These data were plotted versus carbon number, giving a linearcorrelation in the range analyzed (See FIG. 10).

The equation of the line was used to determine response factors for allof the hydrocarbons analyzed (the branching in the C₁₂-C₁₄ dimersgenerated in catalytic reactions is assumed to have negligible effect onthe response).

C₆ 0.5121 C₁₂ 1.1919 C₁₃ 1.3052 C₁₄ 1.4185The response factor for neohexene versus adamantane was established tolie outside this correlation, and was determined independently from twoseparate runs. The response factors were 0.5982 (run 1) and 0.5853 (run2) for an average value of 0.5853.

GC/MS analysis was performed on an HP Model 6890N instrument using anHP5-1 column (30 m length, 25 mm diameter, 0.40 μm film) and an HP 5973mass-selective EI detector.

Dimerization of 1-Hexene Using Dimerization Catalyst

Dimerization catalyst 1 (6.6 mg, 0.016 mmol) was dissolved in 2 mL of astandard solution of 1-hexene (240.8 mM) and adamantane (25.4 mM) inn-heptane in a 4 mL screw-top vial. The vial sealed with a Teflon-linedscrew cap. The mixture was heated briefly with a heat gun to dissolvethe precatalyst and ensure a homogeneous solution. The solution was thensplit into ten aliquots of 0.2 mL each in ten separate 4 mL vialscontaining stir bars. These vials were sealed and stirred at 100° C. inan aluminum block heater (except for one vial representing t₀). Atspecified time intervals, vials were removed from the heat block,immersed in a dry-ice/acetone bath to rapidly cool the contents, andthen diluted with dichloromethane to quench the reaction. Thesesolutions were passed through a short plug of silica gel into a GCautosampler vial, and analyzed by GC. This procedure was repeated threetimes to generate the time profile shown in FIG. 2.

Procedure for Determining Initial Rates of 1-Hexene Dimerization.

Dimerization catalyst 1 (10.0 mg, 0.0240 mmol) was dissolved in 3 mL ofa standard solution of 1-hexene (248, 252, 412, 699, 1010, 2000, or 3996mM) and adamantine internal standard (˜25 mM) in n-decane in a 4 mLscrew-top vial. The vial was sealed with a Teflon-lined screw cap. Themixture was heated briefly with a heat gun and stirred vigorously todissolve the precatalyst and ensure a homogeneous solution. The solutionwas then split into fifteen aliquots of 0.2 mL each in fifteen separate4 mL vials containing stir bars. These vials were sealed and stirred at80, 90, 100, 110, or 125° C. in an aluminum block heater. At specifiedtime intervals, (1, 2, 3, or 4 minutes) vials were removed from the heatblock, immersed in a dry-ice/acetone bath to rapidly cool the contents,and then diluted with dichloromethane to quench the reaction. Thesesolutions were passed through a short plug of silica gel into a GCautosampler vial, and analyzed by GC.

Data for each time point was collected from 3 or 4 different vials,giving 12-15 data points for each initial rate determination. Theconcentrations of both major and minor product isomers were plottedversus time, and the k_(obs) values calculated by linear regressionanalysis (TABLE 1, FIGS. 13, 15, 17, 19, and 21). These data were usedto generate double reciprocal plots for each product isomer at eachtemperature (see FIGS. 14, 16, 18, 20, and 22). These plots were subjectto linear regression analysis to generate slope/intercept values, whichwere used to calculate k₁, K_(eq), and k₂K_(eq)′ according to equations1-8.

$\begin{matrix}{{Rate} = \frac{k_{1}{{K_{eq}\left\lbrack {1 - {Hexene}} \right\rbrack}\lbrack{Ta}\rbrack}_{0}}{1 + {K_{eq}\left\lbrack {1 - {Hexene}} \right\rbrack}}} & (1) \\{{Rate}^{- 1} = {{\frac{1}{k_{1}{K_{eq}\lbrack{Ta}\rbrack}_{0}}\left\lbrack {1 - {Hexene}} \right\rbrack}^{- 1} + \frac{1}{{k_{1}\lbrack{Ta}\rbrack}_{0}}}} & (2) \\{k_{1} = \frac{1}{{b\lbrack{Ta}\rbrack}_{0}}} & (3) \\{K_{eq} = \frac{b}{m}} & (4) \\{{Rate} = \frac{k_{2}{{K_{eq}^{\prime}\left\lbrack {1 - {Hexene}} \right\rbrack}\lbrack{Ta}\rbrack}_{0}}{1 + {K_{eq}\left\lbrack {1 - {Hexene}} \right\rbrack}}} & (5) \\{{Rate}^{- 1} = {{\frac{1}{k_{2}{K_{eq}^{\prime}\lbrack{Ta}\rbrack}_{0}}\left\lbrack {1 - {Hexene}} \right\rbrack}^{- 1} + \frac{K_{eq}}{k_{2}{K_{eq}^{\prime}\lbrack{Ta}\rbrack}_{0}}}} & (6) \\{{k_{2}K_{eq}^{\prime}} = \frac{1}{{m\lbrack{Ta}\rbrack}_{0}}} & (7) \\{K_{eq} = \frac{b}{m}} & (8)\end{matrix}$

TABLE 1 Initial Rate Data (numbers in parentheses are standard errordetermined from regression analysis) Temp. [1-Hexene]₀ k_(obs) Majork_(obs) Minor Entry (° C.) (mM) (10⁻⁵ M s⁻¹) (10⁻⁵ M s⁻¹) 1 80 248 3.06(8) 0.73 (3) 2 80 412 4.85 (10) 1.19 (3) 3 80 699 6.76 (12) 1.59 (4) 480 1010 7.28 (25) 1.77 (7) 5 80 2000 10.76 (44) 2.54 (13) 6 80 399612.42 (55) 2.93 (14) 7 90 248 4.35 (10) 1.23 (4) 8 90 412 7.52 (15) 2.16(6) 9 90 699 10.21 (21) 2.87 (7) 10 90 1010 14.74 (29) 4.10 (8) 11 902000 18.58 (58) 5.11 (19) 12 90 3996 26.70 (58) 7.44 (17) 13 100 2485.87 (10) 1.85 (4) 14 100 252 6.03 (12) 2.00 (5) 15 100 412 9.53 (27)2.98 (10) 16 100 699 16.73 (41) 5.56 (15) 17 100 1010 21.37 (52) 6.77(19) 18 100 2000 37.2 (11) 12.24 (38) 19 100 3996 42.9 (14) 13.76 (48)20 110 248 6.66 (18) 2.42 (7) 21 110 412 10.75 (22) 3.83 (9) 22 110 69918.22 (35) 6.52 (13) 23 110 1010 28.37 (48) 10.17 (19) 24 110 2000 41.7(13) 14.79 (45) 25 110 3996 66.6 (18) 23.78 (71) 26 125 248 8.34 (22)3.62 (11) 27 125 412 14.01 (33) 6.08 (14) 28 125 699 24.65 (76) 10.84(32) 29 125 1010 33.4 (16) 14.32 (65) 30 125 2000 64.3 (34) 28.3 (16) 31125 3996 102.1 (64) 43.0 (30)

Kinetic Fitting Using DynaFit.

The full time course data represented in FIG. 2 was fitted according tothe mechanistic model from Scheme V, as well as terms for alkeneisomerization to cis- and trans-2-hexene, using the freeware kineticsprogram DynaFit. Values for the rate and equilibrium constants k₁,K_(eq), and k₂K_(eq)′ determined at 100° C. were used. All equilibriawere assumed to be rapid. The values of K_(off) and K_(off)′ were set atdifferent values (K_(off)=K_(off)′=1, 2.5, 5, 10, and 15) and thequality of the fit determined by inspection.

Intermediate values of K_(off)≅K_(off)′≅2.5−5 gave the best correlation.Refining K_(off) and K_(off)′ gave values of 4.4(6) and 2.8(9)respectively. Second order rate constants for alkene isomerization weredetermined by fitting according to the equation:Cp*TaCl₂(1-alkene)+1-alkene→Cp*TaCl₂(1-alkene)+2-alkene

-   -   (not an elementary step)

These values are 3.6(2)×10⁻³ M⁻¹ s⁻¹ and 1.8 (2)×10⁻³ M⁻¹ s⁻¹ for theformation of cis- and trans-2-hexene respectively. Presumably thisisomerization occurs via a π-allylic-type mechanism, since the majorcatalyst resting state is the [Ta](1-alkene) complex, rather than aninsertion/β-hydride elimination mechanism; however, due to the lowdegree of isomerization observed, the mechanism of this side-reactionwas not experimentally tested.

Procedure for Determining Initial Rates of 1-Hexene/n-Decane TransferHydrogenation.

Hydrogen transfer catalyst 2 (8.8 mg, 0.0150 mmol) was dissolved in 3 mLof a standard solution of 1-hexene (248, 412, 699, or 1010 mM) andadamantine internal standard (˜25 mM) in n-decane in a 4 mL screw-topvial. The solution was stirred to dissolve the precatalyst and ensure ahomogeneous solution. The solution was then split into fifteen aliquotsof 0.2 mL each in fifteen separate 4 mL vials containing stir bars.These vials were sealed and stirred at either 100 or 125° C. in analuminum block heater. At specified time intervals, (10, 20, 30, or 40minutes) vials were removed from the heat block, immersed in adry-ice/acetone bath to rapidly cool the contents, and then diluted withdichloromethane to quench the reaction. These solutions were passedthrough a short plug of silica gel into a GC autosampler vial, andanalyzed by GC.

Data for each time point was collected from 3 or 4 different vials,giving 12-15 data points for each initial rate determination. Theconcentrations of n-hexane and the 2-hexenes (combined) were plottedversus time, and the k_(obs) values calculated by linear regressionanalysis (See FIG. 23 and FIG. 24). These rate data were then plottedversus [1-hexene]₀ (see FIG. 25).

Heating a solution of 1-hexene (248 mM) and hydrogen transfer catalyst 2(5 mM) in n-decane leads to the generation of several products that canbe analyzed by GC (Scheme VI).

In the C₆ fraction, n-hexane (from transfer hydrogenation) and internalhexenes (from alkene isomerization) are observed. C₁₀ alkenes are alsoobserved (including 1-decene), but accurate quantification of thesespecies is not reliable due to overlap with the large signal forn-decane solvent. Therefore, the formation of n-hexane and internalhexenes has been monitored to generate initial rate data for transferhydrogenation and alkene isomerization respectively (Table 2).

TABLE 2 Initial Rate Data for 1-Hexene/n-Decane Transfer Hydrogenationand 1-Hexene Isomerization Catalyzed by 2. [1-Hexene]₀ Temp.k_(obs)(hydrog) k_(obs)(isom) Entry (mM) (° C.) (10⁻⁵ M s⁻¹)^(a) (10⁻⁵ Ms⁻¹)^(a) 1 248 100 1.26 (5) 1.00 (4) 2 412 100 0.753 (38) 1.53 (5) 3 699100 0.572 (20) 2.31 (7) 4 1010 100 0.387 (10) 2.79 (6) 5 248 125 12.4(4) 4.73 (20) 6 412 125 8.85 (23) 6.30 (16) 7 1010 125 2.88 (14) 11.8(5) ^(a)Numbers in parenthesis are standard error from regressionanalysis.

Analysis of the initial rates of transfer hydrogenation andisomerization versus [1-hexene]₀ reveals that transfer hydrogenation isinverse order in [1-hexene] from 248-1010 mM, whereas isomerization ispositive order in [1-hexene], exhibiting saturation behavior (see FIG.6). The inverse dependence on [1-hexene] is consistent with previouswork on cyclooctane/tert-butylethylene (TBE) transfer hydrogenationcatalyzed by hydrogen transfer catalyst 2: the rate is first order in[TBE] at low concentrations (where the Ir dihydride F is the majorresting state), and inverse order at higher concentrations. Whileinhibition by TBE is due to reversible oxidative addition/reductiveelimination of a vinyl C—H bond, linear alpha olefins (LAOs, such as1-hexene) inhibit catalysis by competitive formation of the 1-alkenecomplex G. Indeed, G (where the alkene is 1-octene) is reportedly amajor resting state in TBE/n-octane transfer hydrogenation. Thus, athigher [1-hexene], the equilibrium in Scheme VII would be shifted towardG, which is not on the transfer

This shift in equilibrium between resting states is also consistent withthe observation that the transfer hydrogenation rate is affecteddramatically by temperature, increasing nearly 10-fold from 100-125° C.(see Table 2, entries 1 and 5). The equilibrium in Scheme VII is a3-into-2 reaction, which means that the reverse direction isentropically favored; thus, an increase in temperature would shift theequilibrium toward F, which is an on-cycle intermediate for transferhydrogenation. Furthermore, since G is also an active catalyst foralkene isomerization, this shift should decrease the rate ofisomerization relative to transfer hydrogenation. This is exactly thecase, where with an initial [1-hexene] of 248 mM,k_(obs)(hydrog)/k_(obs)(isom) is 1.26 at 100° C. and 2.62 at 125° C. Ofcourse, temperature effects on the other steps of both catalytic cycleswill influence these rates as well.

Notably, the determination that isomerization is positive order in[1-hexene] (from initial rate data) is in contrast to the zero orderdependence previously reported for alkene isomerization catalyzed byhydrogen transfer catalyst 2 (observation over 5 half-lives with initial[1-alkene]=100 mM). This reaction proceeds by a n-allylic mechanism thathas a unimolecular turnover-limiting step and thus should be zero orderin [1-alkene]; however, the positive order dependence observed here canbe explained in terms of the equilibrium between resting states inScheme VII. As the concentration of 1-hexene is increased, the steadystate concentration of G will increase, leading to a higher rate ofalkene isomerization. Thus, increasing [1-hexene] not only inhibitstransfer hydrogenation, it also favors the undesirable alkeneisomerization pathway. The trend toward saturation in the rate of1-hexene isomerization shown in FIG. 6 is entirely consistent with aunimolecular turnover-limiting step in the n-allylic isomerizationcatalytic cycle.

Implications for Tandem Catalytic Alkane/Alkene Coupling.

The diametrically opposed kinetic trends in alkene dimerizationcatalyzed by dimerization catalyst 1 and transfer hydrogenationcatalyzed by hydrogen transfer catalyst 2 is a major factor in thehomogeneous tandem catalytic coupling of 1-hexene and n-heptane. As formany other one-pot dual catalyst processes, the optimal conditions forthe individual catalysts do not necessarily translate into the optimalconditions for the pair. While dimerization catalyst 1 operates mostefficiently at lower temperatures and high substrate loading, hydrogentransfer catalyst 2 works best at high temperatures and low substrateloading. Thus, in order to best match the rates of the two individualreactions, tandem catalysis is effective at a moderate temperature (100°C.) and an alkene concentration that is as low as possible. In terms ofsimple batch reactions, the initial optimization led to a 1-hexeneloading of ˜250 mM (see TABLE 3, entry 1).

TABLE 3 Temperature and Concentration Effects on 1-Hexene/n-HeptaneCoupling by 1 and 2.

[1-Hexene] ₀ [1]/[2] Temp. n-Hexane C₁₂ C₁₃/C₁₄ TON TON Coop. Entry (mM)(mM) (° C.) (mM) ^(a) (mM) ^(a) (mM) ^(a) for 1^(b) for 2^(b) (%) 1  2508/5 100  52  81 13/10 13 (3) 10 (6) 63 2  500 8/5 100  88 193 15/10 27(3) 18 (7) 40 3 1000 8/5 100  87 432 18/10 58 (4) 17 (8) 45 4  250 8/5125 106  58 15/13 11 (4) 21 (8) 39 5  500 8/5 125 140 162 24/14 25 (5) 28 (10) 37 6 1000 8/5 125 161 386 32/14 54 (6)  32 (12) 38 7  250 8/5150 147  39 12/12  8 (3) 29 (7) 24 8  500 8/5 150 216 128 26/15 21 (5) 43 (11) 27 9 1000 8/5 150 ^(a) Determined by GC/FID using adamantane asan internal std., avg. of at least 2 runs. ^(b)TONs in parentheses arefor production of C₁₃ + C₁₄.

Raising the substrate loading to 500 or 1000 mM merely results in theproduction of more C₁₂ homodimer, with little additional tandemcatalysis observed (see entries 2 and 3 of Table 3); this is due to thepositive order dependence on [1-hexene] for dimerization catalyst 1, andthe inverse order dependence on [1-hexene] for hydrogen transfercatalyst 2. Conversely, raising the temperature to 125° C. or 150° C.dramatically reduces catalyst cooperativity (entries 4 and 7 of Table3), due to the much stronger temperature dependence exhibited byhydrogen transfer catalyst 2 relative to dimerization catalyst 1.

While increasing [1-hexene] or temperature results in a rate imbalancebetween the two catalysts, it is possible that increasing both of thesevariables would have complementary effects, allowing a higher degree oftandem catalysis at increased substrate loading

Procedure for Styrene Dimerization Using Dimerization Catalyst 1.

Dimerization Catalyst 1 (10.4 mg, 0.025 mmol), styrene (53.5 mg, 0.514mmol), and mesitylene (internal standard, 10.8 mg, 0.0898 mmol) weredissolved in C₆D₆ (1 mL). This solution was then transferred into two J.Young NMR tubes. Initial ¹H NMR spectra were recorded (see FIG. 27), andthen the tubes were heated to 110° C. in an oil bath. After set timeintervals, the tubes were removed from the oil baths and new spectraacquired, until ˜95% conversion was reached (about 72 h, see FIG. 28).NMR yields were determined in the following manner: The area of thesignal for the three aromatic protons of the mesitylene internalstandard (˜6.75 ppm) was set at 25.00. The areas of the peaks for thetwo terminal alkene protons of styrene were determined in the initialspectra, as well as the areas of the two peaks for the vinylideneprotons of the major product at 72 hours. The ratios of these valueswere determined, giving four measurements of the yield. These valueswere averaged for each run, and then these two values were averagedagain to give a final NMR yield of ˜88%. The peaks for the minorregioisomer (d, 3H, 1.23 ppm, CH₃; m, 1H, 3.25 ppm, —CH(CH₃)Ph) werealso integrated in the 72 h spectra, giving an average NMR yield of ˜2%.

NMR yields:

Run 1: 82.8%; 89.3%; 85.6%; 92.3%. Average: 87.5% (Minor isomer: 2.3%)

Run 2: 84.4%; 86.3%; 90.9%; 92.9%. Average: 88.6% (Minor isomer: 2.3%)

Once NMR yields were established, the two samples were combined anddiluted with dichloromethane to a total volume of ˜4 mL. Adamantane(16.2 mg, GC standard) was added, and the mixture analyzed by GC (seeFIG. 26). The yield of both major and minor styrene dimers wasdetermined to be 81% (major) and 2% (minor).

Heating a 500 mM solution of styrene in C₆D₆ with 25 mM dimerizationcatalyst 1 to 110° C. does in fact lead to dimerization, albeit slowly(t_(1/2)˜14 h, see Scheme VIII). By ¹H NMR spectroscopy and GC analysis,there is one major product of this reaction, the “head-to-tail” dimerformed. Interestingly, there is a complete switch in regioselectivityfrom reactions with LAOs; the “tail-to-tail” product in styrenedimerization is formed.

Procedure for Monitoring Dimerization of Styrene Over Four Half Lives.

Dimerization catalyst 1 (6.6 mg, 0.016 mmol), styrene (53.0 mg, 0.509mmol), and 1,3,5-trimethoxybenzene (internal standard, 1.6 mg) weredissolved in C₆D₆ (2 mL). This solution was then split evenly into fourJ. Young NMR tubes. Initial ¹H NMR spectra were recorded, and then thetubes were heated to either 100° C. (two tubes) or 125° C. (two tubes)in an oil bath. After set time intervals, the tubes were removed fromthe oil baths and new spectra acquired, until ˜4 half lives had passed.The three aromatic protons of the 1,3,5-trimethoxybenzene internalstandard (˜6.25 ppm) were integrated versus the terminal vinylic protonof styrene that is cis relative to the phenyl group (5.6 ppm), with theformer area set at 25.00. The concentration of styrene at each timepoint was determined by the following formula, wherein[Styrene]_(0=0.255) M; I=area of vinylic signal @5.6 ppm; and I₀=initialarea of vinylic signal @5.6 ppm:[Styrene]=[Styrene]×(I/I ₀)The dimerization of Styrene was evaluated by ¹H NMR over various timepoints (see FIGS. 29-32).

Initial Rates of Styrene/1-Heptene Co-Dimerization Using DimerizationCatalyst 1.

Dimerization catalyst 1 (10.1 mg, 0.0243 mmol), styrene (97.7 mg, 0.938mmol), 1-heptene (76.0 mg, 0.774 mmol), and adamantane (internalstandard, 12.0 mg, 0.088 mmol) were dissolved in 2.8 mL of n-decane in a4 mL screw-top vial containing a Teflon-coated stir bar. The vial wassealed with a Teflon-lined screw cap and the contents stirred vigorouslyto ensure complete dissolution of dimerization catalyst 1. The solutionwas then split into fifteen aliquots of 0.2 mL each in fifteen separate4 mL vials containing stir bars. These vials were sealed and stirred at100° C. in an aluminum block heater. At specified time intervals, (1, 2,3, or 4 minutes) vials were removed from the heat block, immersed in adry-ice/acetone bath to rapidly cool the contents, and then diluted withdichloromethane to quench the reaction. These solutions were passedthrough a short plug of silica gel into a GC autosampler vial, andanalyzed by GC.

Data for each time point was collected from 3 different vials, giving 12data points for each initial rate determination. The concentrations ofthe 1-heptene dimers (both regioisomers combined), and the co-dimers(all isomers combined) were plotted versus time, and the k_(obs) valuescalculated by linear regression analysis (see FIG. 35). In order tonormalize for the different concentrations of 1-heptene and styreneused, the initial rate for styrene dimerization was multiplied by afactor of 0.825 (the ratio of [1-heptene]₀/[styrene]₀), giving aninitial rate ratio of 4.05:1 for 1-heptene dimerization versusstyrene/1-heptene co-dimerization. Styrene dimers were not observedunder these conditions.

Procedure for Co-Dimerization of Styrene/1-Heptene Using DimerizationCatalyst 1.

Dimerization catalyst 1 (20.4 mg, 0.050 mmol), styrene (52.1 mg, 0.500mmol), 1-heptene (49.0 mg, 0.499 mmol), and adamantane (internalstandard, 10.2 mg, 0.075 mmol) were dissolved in 2 mL of n-heptane in a4 mL screw-top vial containing a Teflon-coated stir bar. The vial wassealed with a Teflon-lined screw cap and the contents stirred at 100° C.in an aluminum block heater. After 18 hours, the vial was removed, andthe contents diluted with dichloromethane to a total volume of ˜4 mL.This solution was passed through a short plug of silica gel beforeanalysis by GC and GC/MS (see FIGS. 36-42).

Synthesis of Authentic Co-Dimers:

(1-Methyl-2-methylene-octyl)-benzene was prepared by Ni-catalyzedcoupling of 1-heptene and styrene according to Ho et al., Angew. Chem.Int. Ed. 49:9182 (2010). Briefly: Under an N₂ atmosphere, Ni[COD]₂ (27.5mg, 0.10 mmol) and1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene (IPr,38.9 mg, 0.10 mmol) were dissolved in toluene (4 mL) in a reaction tubeand stirred for ˜1 hour. An aliquot of 1-heptene (˜28 μL) was added,followed by the addition of triethylamine (60.7 mg, 0.60 mmol),p-anisaldehyde (13.6 mg, 0.10 mmol), and TESOTf (52.9 mg, 0.20 mmol).The solution was stirred for ˜15 minutes. Finally, styrene (208.3 mg,2.00 mmol) and 1-heptene (589.1 mg, 6.00 mmol) were added, and thesolution was stirred for ˜24 hours at room temperature under N₂. Thecontents were then exposed to air and diluted with hexanes (˜10 mL). Themixture was filtered through a short silica plug, followed by elution ofthe solid with 20% EtOAc in hexanes (˜25 mL). The solvent wasevaporated, and the residue dissolved in dichloromethane. The productsolution was analyzed by GC and GC/MS (see FIGS. 43-46). Theregiochemistry of the major co-dimer was definitively established by Hoet al., as well as the regiochemistry of styrene homodimerization. Thisco-dimer solution was co-injected with the co-dimer mixture generated bydimerization catalyst 1 (see FIG. 47).

Procedure for Monitoring Styrene/n-Heptane Coupling Reactions Over Time:

Dimerization catalyst 1 (6.6 mg, 0.016 mmol) and 2 (17.7 mg, 0.030 mmol)were dissolved in 2 mL of a standard solution of styrene (250 mM) andadamantane (25.3 mM) in n-heptane in a 4 mL screw top vial containing aTeflon-coated stir bar. The vial was sealed with a Teflon-lined screwcap. The mixture was heated to 100° C. for ˜30 seconds in an aluminumblock heater inside an argon-filled glovebox to dissolve theprecatalysts and ensure a homogeneous solution, and then immediatelycooled to −35° C. in the freezer. An aliquot (˜0.1 mL, representing t₀)was removed and placed into a GC autosampler vial; this aliquot was thendiluted with dichloromethane to a total volume of ˜1 mL before analysisby GC.

The reaction mixture was heated to 100° C. in the aluminum block heater,and at specified times (1, 2, 3, 4, 5, 6, 7, 8, 10, 12, and 18 hours)the vial was removed and cooled to −35° C. in the freezer before takingan aliquot for analysis by GC. The concentrations of all major specieswere then plotted versus time to give time course profiles of the tandemreaction (see FIG. 48). The effects of the cooperativity inStyrene/n-Heptane Coupling by dimerization catalyst 1 and hydrogentransfer catalyst 2 is presented in Table 4.

TABLE 4 Evaluation of Catalyst Cooperativity in Styrene/n-HeptaneCoupling by 1 and 2.

Styrene Co- Heptane [Styrene] ₀ [1]/[2] Time Temp. % EB Dimer DimersDimers Ton Ton Coop. Entry (mM) (mM) (h) (° C.) Conv. (mM) ^(a) (mM)^(a) (mM) ^(a) (mM) ^(a) for 1^(b) for 2^(b) (%)  1 250 8/5 18 100 62 70  23 23 11 7 (4) 14 (9)  63  2 250 8/5 48 100 75  71  35 28 12 9 (5)14 (10) 72  3 250 5/8 18 100 78 132  11 27 26 13 (11) 17 (10) 60  4 250 5/10 18 100 89 162  8 26 35 14 (12) 16 (10) 60  5 250 10/10 18 100 99163  17 31 42 9 (7) 16 (11) 70  6 250 10/15 18 100 99 192  6 24 46 8 (7)13 (8)  60  7 250  8/15 18 100 99 202  4 20 44 8 (8) 13 (7)  53  8 100010/15 72 100 67  99 229 42  4 27 (5)  7 (3) 50  9 250 10/15 18 125 99215  2 15 38 5 (5) 14 (6)  42 10 250 10/15 18 150 >99  209  2 14 36 5(5) 14 (6)  41 ^(a) Determined by GC/FID using adamantane as an internalstd., avg. of at least 2 runs. ^(b)TONs in parentheses are forproduction of co-dimers + heptane dimers.

Procedure for Monitoring Styrene/n-Heptane Transfer Hydrogenation OverTime:

Hydrogen transfer catalyst 2 (17.7 mg, 0.030 mmol) was dissolved in 2 mLof a standard solution of styrene (250 mM) and adamantane (25.3 mM) inn-heptane in a 4 mL screw top vial containing a Teflon-coated stir bar.The vial was sealed with a Teflon-lined screw cap. The mixture washeated to 100° C. for ˜30 seconds in an aluminum block heater inside anargon-filled glovebox to dissolve the precatalysts and ensure ahomogeneous solution, and then immediately cooled to −35° C. in thefreezer. An aliquot (˜0.1 mL, representing t₀) was removed and placedinto a GC autosampler vial; this aliquot was then diluted withdichloromethane to a total volume of ˜1 mL before analysis by GC.

The reaction mixture was heated to 100° C. in the aluminum block heater,and at specified times (1, 2, 3, 4, 5, 6, 7, 8, 10, 12, and 18 hours)the vial was removed and cooled to −35° C. in the freezer before takingan aliquot for analysis by GC. The concentrations of styrene andethylbenzene were then plotted versus time to give time course profilesof the transfer hydrogenation reaction. These data were overlaid on thestyrene/ethylbenzene concentrations from the tandem reaction (see FIG.49).

Results of Styrene Dimerization and Styrene/1-Heptene Co-DimerizationCatalyzed by Dimerization Catalyst 1.

In the catalytic coupling of 1-hexene/n-heptane, competitivehomodimerization of 1-hexene is prevalent; even with slow addition of1-hexene by syringe pump, the C₁₂ fraction represents 50% of the highermolecular weight products. In an effort to minimize this side reaction,TBE was initially examined as a possible sacrificial hydrogen acceptorthat would not be incorporated into the dimerization catalytic cycle,enabling the catalytic dimerization of alkanes.

While modest yield was achieved with TBE, poor conversion and suspectedcatalyst decomposition led to the consideration other hydrogenacceptors. Styrene is an attractive alternative, since competitivealkene isomerization would be avoided. Furthermore, the ethylbenzenegenerated during transfer hydrogenation could, in principle, beregenerated by dehydrogenation (steam cracking), which is practicedindustrially on a large scale to synthesize styrene monomer.

In previously reported studies, the stoichiometric and catalytic alkenedimerization by dimerization catalyst 1 and related complexes was notreported for the dimerization of styrenes. While the Cp*TaCl₂(styrene)complex was prepared and characterized, attempts to observemetallacycles derived from two styrene units, or styrene and analiphatic alkene, were unsuccessful. These observations (or rather lackthereof) were encouraging in the context of tandem catalysis, ascompetitive dimerization of the hydrogen acceptor (i.e. styrene) shouldbe minimized.

Monitoring the dimerization of styrene under conditions analogous totandem catalysis (250 mM styrene, 8 mM dimerization catalyst 1, 100° C.)reveals strict exponential decay of styrene up to ˜3.5 half-lives, witht_(1/2)=40 h (see FIG. 7); deviation from linearity at high conversionis likely due to product inhibition, as observed for 1-hexenedimerization. This first order dependence on [styrene] is consistentwith a mechanism analogous to the top catalytic cycle in Scheme V, wherethe equilibrium of:Cp*TaCl₂(styrene)+styrene

Cp*TaCl₂(metallacycle)

-   -   (with equilibrium constant K_(eq)″)        heavily favors reactants, which is in accord with the inability        to observe metallacycles derived from styrenes. The observed        first order rate constant k_(obs)=K_(eq)″k₃[Ta]₀, and therefore        K_(eq)″k₃=6.00(6)×10⁻⁴ M⁻¹ s⁻¹ (where k₃ is the rate constant        for the unimolecular decomposition of the styrene metallacycle,        analogous to k₂ in Scheme V). Comparing K_(eq)″k₃ to the        corresponding values for 1-hexene dimerization to the major and        minor isomers gives a ratio of 53:17:1        (K_(eq)k₁:K_(eq)′k₂:K_(eq)″k₃); thus 1-hexene dimerization is        ˜70× faster than styrene dimerization.

The markedly slower dimerization of styrene relative to 1-hexene meansthat styrene should be useful as a sacrificial hydrogen acceptor intandem catalysis; however, co-dimerization of styrene and the alkane isanother likely product. In order to determine the relative rates of LAOdimerization relative to styrene/LAO coupling, a mixture of styrene (313mM) and 1-heptene (258 mM) was dimerized with dimerization catalyst 1.Under initial rate conditions, 1-heptene dimerization is 4× faster than1-heptene/styrene co-dimerization. Notably, under these conditions1-heptene dimerization is 2.8× slower than 1-hexene dimerization in theabsence of styrene. Clearly, the presence of styrene inhibits LAOdimerization, probably because Cp*TaCl₂ (styrene) is a significantresting state, which could be a complicating factor in achieving a highdegree of tandem catalysis.

Analysis of the GC traces of these initial rate experiments indicatedthat there are multiple styrene/1-heptene co-dimer products. Running a1-heptene/styrene co-dimerization to completion gives 1-heptene dimers,co-dimers, and styrene dimer. By GC, there appear to be three or fourco-dimers (one peak has a consistent shoulder), with one major species.If both “tail-to-tail” and “head-to-tail” regioisomers are considered,there are four possible products (Scheme IX).

Other embodiments, combinations and modifications of the compositionsand methods presented herein will occur readily to those of ordinaryskill in the art in view of these teachings. Therefore, the compositionsand methods are to be limited only by the following claims, whichinclude all such embodiments and modifications when viewed inconjunction with the above specification and accompanying drawings.

The invention claimed is:
 1. A method of coupling a n-alkane reactantwith a n-alkene reactant so as to form one or more branched alkeneproducts in a single stage tandem process, comprising: coupling an-alkane reactant with a n-alkene reactant in the presence of a catalystcomprising: (i) a hydrogen transfer catalyst and (ii) an alkenedimerization catalyst so as to generate one or more branched alkeneproducts, wherein the molecular weight of the one or more branchedalkene products is greater than the molecular weight of the n-alkanereactant and greater than the molecular weight of the n-alkene reactant;wherein the hydrogen transfer catalyst is an iridium pincer complexcatalyst and the alkene dimerization catalyst is a tantalum catalystthat is selective for the formation of dimer products comprising astructure of Formula II:

wherein Z is either 1 or 2; n is an integer from 1 to 5; each Y isindependently selected from the group consisting of D, H, optionallysubstituted C₁-C₆ alkyl, silane, and C₁-C₄ alkylsilane; Y¹ is selectedfrom the group consisting of H, D, halo, ═S, ═O, PMe₃, and ═C(H)(CMe₃);Y² is selected from the group consisting of H, D, halo, ═S, ═O, andPMe₃, or Y² is absent; R² is selected from the consisting of H, aryl,optionally substituted C₁-C₁₅ alkyl, and optionally substituted C₁-C₁₅hetero-alkyl; and R³ is selected from the group consisting of H, aryl,optionally substituted C₁-C₁₅ alkyl, and optionally substituted C₁-C₁₅hetero-alkyl, wherein the one or more branched alkene products compriseone or more carbon atoms from both the n-alkane reactant and then-alkene reactant.
 2. The method of claim 1, wherein both the hydrogentransfer catalyst and the alkene dimerization catalyst are heterogeneouscatalysts.
 3. The method of claim 1, wherein the alkene dimerizationcatalyst comprises a structure of Formula II(a):

wherein, R² is selected from the group consisting of aryl, optionallysubstituted C₁-C₁₅ alkyl, and optionally substituted C₁-C₁₅hetero-alkyl.
 4. The method of claim 1, wherein the hydrogen transfercatalyst comprises a structure of Formula I:

wherein, each R is independently H or a C₁-C₃₀ hydrocarbyl radical; eachR¹ is independently a C₁-C₃₀ hydrocarbyl radical; and each X isindependently an O or CH₂.
 5. The method of claim 1, wherein thehydrogen transfer catalyst comprises a structure of Formula I(a):


6. The method of claim 1, wherein the hydrogen transfer catalyst isimmobilized on a solid support, wherein the coupling is carried out in asolvent, and wherein the method further comprises the step of separatingfree hydrogen transfer catalyst from the solvent.
 7. The method of claim1, wherein the n-alkane reactant is a C₅-C₁₀ n-alkane.
 8. The method ofclaim 1, wherein the n-alkene reactant is a C₅-C₁₀ n-alkene.
 9. A methodfor coupling a first n-alkane reactant with a second n-alkane reactantto form one or more branched alkene products, comprising: coupling thefirst n-alkane reactant with the second n-alkane reactant using styreneas a sacrificial hydrogen acceptor in the presence of a catalystcomprising: (i) a hydrogen transfer catalyst and (ii) an alkenedimerization catalyst so as to generate one or more branched alkeneproducts, wherein the molecular weight of the one or more branchedalkene products is greater than the molecular weight of the firstn-alkane reactant and greater than the molecular weight of the secondn-alkane reactant; wherein the hydrogen transfer catalyst is an iridiumpincer complex catalyst and the alkene dimerization catalyst is atantalum catalyst that is selective for the formation of dimer productscomprising a structure of Formula II:

wherein, Z is either 1 or 2; n is an integer from 1 to 5; each Y isindependently selected from the group consisting of D, H, optionallysubstituted C₁-C₆ alkyl, silane, and C₁-C₄ alkylsilane; Y¹ is selectedfrom the group consisting of H, D, halo, ═S, ═O, PMe₃, and ═C(H)(CMe₃);Y² is selected from the group consisting of H, D, halo, ═S, ═O, andPMe₃, or Y² is absent; R² is selected from the group consisting of H,aryl, optionally substituted C₁-C₁₅ alkyl, and optionally substitutedC₁-C₁₅ hetero-alkyl; and R³ is selected from the group consisting of H,aryl, optionally substituted C₁-C₁₅ alkyl, and optionally substitutedC₁-C₁₅ hetero-alkyl, wherein the one or more branched alkene productscomprise carbon atoms from both the first n-alkane reactant and thesecond n-alkane reactant.
 10. The method of claim 9, wherein the firstn-alkane reactant and the second n-alkane reactant have the samestructure.
 11. The method of claim 9, wherein the first n-alkanereactant and the second n-alkane reactant do not have the samestructure.
 12. The method of claim 9, wherein both the hydrogen transfercatalyst and the alkene dimerization catalyst are heterogeneouscatalysts.
 13. The method of claim 9, wherein the alkene dimerizationcatalyst comprises a structure of Formula II(a):

wherein, R² is a phenyl.
 14. The method of claim 9, wherein the hydrogentransfer catalyst comprises a structure of Formula I:

wherein, each R is independently a H or a C₁-C₃₀ hydrocarbyl radical;each R¹ is independently a C₁-C₃₀ hydrocarbyl radical; and each X isindependently an O or CH₂.
 15. The method of claim 9, wherein thehydrogen transfer catalyst comprises a structure of Formula I(a):


16. The method of claim 9, wherein the hydrogen transfer catalyst isimmobilized on a solid support, wherein the reaction is carried out in asolvent system, and wherein the method further comprises the step ofseparating free hydrogen transfer catalyst from the solvent system. 17.The method of claim 16, wherein the solvent system comprises the firstn-alkane reactant and/or the second n-alkane reactant.
 18. The method ofclaim 9, wherein the first n-alkane reactant and the second n-alkanereactant are C₅-C₁₀ n-alkanes.
 19. The method of claim 1, wherein themethod further comprises hydrogenating or reducing the one or morebranched alkene products to one or more branched alkane products. 20.The method of claim 9, wherein the method further compriseshydrogenating or reducing the one or more branched alkene products toone or more branched alkane products.
 21. The method of claim 1, whereinthe n-alkane reactant is n-heptane and the n-alkene reactant is 1-hexeneand the one or more alkene products are C₁₂-C₁₄-branched alkeneproducts.